Crotonic acid, 3-hydroxy-cis, diester of unsaturated alkylene, bis(dialkyl phosphate)



United States Patent ()ihce 3,366,713 Patented Jan. 30, 1968 3,366,713 CROTONIC ACID, 3 YDROXY CH5, DIESTER F UNSATURATED ALKYLENE, BIS(DIALKYL PHOSPHATE) crotonic acid, 3-hydroxy-, cis, Z-butynylene bis (ester) bis(di( chloromethyl) phosphate) crotonic acid, 3-hydroxy-, cis, Z-butynylene bis(ester),

bis di brom'oethyl phosphate) Juan G. Morales, Modesto, Calif., assignor to Shell Oil 5 crotonic acid, 3-hydroXy-, cis, Z-butynyIene bis(ester),

Company, New York, N.Y., a corporation of Delaware bis (methyl chloromethyl phosphate) N0 Drawillg- Filed N O- 4, crotonic acid, 3-hydroxy-, cis, Z-butenylene bis(ester),

150 Chums- 1 bis(diethyl phosphate) v crotonic acid, 3-hydroXy-, cis, Z-butenylene bis(ester), ABSTRACT OF THE DISCLOSURE 10 crci t r i d c igg liiig iig ibis, 2-butenylene bis(ester), Insecticidal bis-esters of crotonic acid phosphates such bis(di('chloromethyl) phosphate) as crotonic acid, 3-hydroxy-, cis, Z-butynylene bis(ester), crotonic acid, 3-hydroXy-, cis, 2-octynylene bis (ester), bis(dimethyl phosphate). bis (diethyl phosphate) CICglOlgCglCldi 3i1hYdLOXYS, cis, 2-octynylene bis (ester), is i uty p osp ate This invention relates to novel organophosphorus comcrotonic acid, 3-hydroXy-, cis, 2-octynylene bis (ester), pounds which have been found to be effective for the bis(di(chlorortnethyl)phosphate) I control of insects. crotonic acid, 3- y.droXy-, cis, diester with 2,7-dimethy It has been found that crotonates represented by the 3,5-octadiyne-Z,7-diol, bis(diethyl phosphate) formula: crotonic acid, 3-hydroxy-, cis, diester with 2,7-dimethyl- H H O 3,5-octadiyne-2,7-diol, bis(di(chloromethyl) phosphate) t 1 1* crotonic acid, 3-hydroxy-, cis, Z-octenylene bis(ester), f- -ff f bis(dimethyl phosphate) 0 CH3 crotonic afidl, 3l-lhydgoxyi, cis, 2-octenylene bis(ester), is diet W p osp ate wherein R represents alkyl of one to four carbon atoms crotonic acid, cis, zoctenylene bis(ester), or haloalkyl of one to four carbon atoms and R reprebis(dibutylphosphate) Sents alkenylene. or i i p up eight carbon crotonic acid,3-hydroxy-,cis,3-chlor0,2-butylene bis atoms, are efl ective miticides and insecticides. When ap- (ester), b1s( dimethyl phosphate) plied to crops at dosages which will effectively control crotonic acid, 3-hydroxy-, ClS, 3-chloro, Z-butenylene mltes and msects, the compounds of the inventlon are 1s(ester),b1s(d1methyl phosphate) IlOIl-lIlJllflOLlS to the plants so treated. Thls comblnation crotonic acid, 3-hydroxy-, ClS, 3-bromo, 2-octynylene of a high order of efiectiveness at low dosages and absence bi (est r) bi (dimeth I h s h t of phytotoxicity to the crop to be protected makes the S e S y p o p a e crotonates of the invention attractive candidates in the The compoundsdofb the inventioln wherein R is 1methyl field of plant protection. are to be preferre ecause o t eir outstandingy high The compounds of the invention, characterized by the insecticidal activity. attachment of an unsaturated moiety to the carbonyl Preferred because of their particular insec cidal propfunction of the molecule, have surprising and unexerties are those bis esters of the invention wherein R pectedly high toxicity to lepidopterous larvae. The subrepresents butenylene, butynylene or octynylene. Exemject compounds are also highly useful for the control of plary of such crotonic acid diesters are crotonic acid, 3- phytophagous mites and mites of medical importance Y S, cis, z-blltynylene bis(dim'eihyl P especially those mites which transmit disease. In addition phate), crotonic acid, 3-hydroXy-, cis, 2-butenylene bis these crotonates are also toxic to several other species (ester), bis(dimethyl phosphate) and crotonic acid, 3- of economically important insects, including aphids. hydro y-, CiS diesief With Y ,5- d y -2,

In the crotonates of the invention, R suitably is either diol, bis(dirnethyl phosphate). straight-chain or branched-chain alkyl or middle halogen- The alkenyl diesters of the invention are'conveniently substituted alkyl (preferably mono-halogen-substituted) prepared by a reaction between alkenylic diols and diof one to four carbon atoms. R suitably is an unsubstialkyl phosphates of 3-hydroxy crotonyl halides in the tuted or mono (middle-halogen)-s-ubstituted alkenylene or presence of an acid catalyst to yield the reaction product alkynylene moiety of up to eight carbon atoms, which CC d g to the qu i n:

OH; H O 0 CH3 H O HOalkenyleneOI-I (alkyl O l OO=( 3 3halogeu [(afryl O I OC7=( J-alkenylene A )2 .12 may be stralghtor branched-chain, in Which the unsatu- Preparation of Such dialkyl phosphates of 3 hydmxy IGUOIIPCCUIS between any two carbon atoms of the chain crotonyl halides is disclosed in copmding application Ser excepting the carbon atoms bonded to the oxygen atom of 441,861 filed Man 22, 1965. the O.Xy'carb0nyl i By mlddle halogen 1S meant so The reaction is started at temperaturessli-ghtly above chlorme and i I room temperature (3040 C.). The addition of the more Examples of thls new class of crotonates Include: heat is made slowly to avoid any undue temperature rise crotonic acid, 3-hydroXy-, cis, Z-butynylene bis(ester), to this mildly exothermic reaction. The desired temperabis(diethyl phosphate) ture range of the reaction is between 70-100 C. crotonic acid, 3-hydroxy-, cis, 2-butynylene bis(ester), The alkynyl compounds of the invention may be conbis (dipropyl phosphate) crotonic acid, 3hydroXy-, cis, 2-butynylene bis(ester),

bis (dibutyl phosphate) CHsH O veniently prepared by the addition of a diol containing an alkynyl group to the halide of an appropriate crotonic acid according to the schematic equation:

The following examples are offered to illustrate how certain select compounds of the invention are synthesized and to illustrate their activity to some species of mites and insects. These examples are nOt to be construed as in any way limiting the scope of the invention. In the following examples, the parts given are by weight unless otherwise noted.

EXAMPLE I (A) Preparation of 3-(dimethoxyphosphinyloxy) crotonic acid 942 parts of technical (92%) alpha-methylbenzyl ester of 3-(dimethoxyphosphinyloxy)crotonie acid was placed in an autoclave, together with 40 parts of palladized charcoal, parts by volume of glacial acetic acid and 2000 parts by volume of methanol. The reactor was pressurized with hydrogen and the mixture stirred for 4 hours at a temperature of about 35 C. The reactor then was vented, parts of fresh palladized charcoal were added, and repressurized with hydrogen and the mixture stirred for an additional 8.5 hours at about 25-35 C. The catalyst then was filtered off, and the methanol stripped off at 0 C., 0.45 Torr, then at 65 C., 0.4 Torr. The product then was recrystallized from anhydrous ether at 65 C., then was stripped to C., 0.5 Torr, to give 3 (dimethoxyphosphinyloxy)crotonic acid (equivalent weight 209 grams-equiv; calculated for PO C H :21O).

(B) Preparation of 3-(dimethoxyphosphinyloxy) crotonyl chloride 400 parts of 3-(dirnethoxyphosphinyloxy) crotonic acid, prepared as in A, was dissolved in 400 parts by volume of methylene chloride, 261 parts of thionyl chloride in 260 parts by volume of methylene chloride was added dropwise with stirring over a 45 minute period, the temperature being maintained at 38-40 C.; the mixture then was refluxed C.) for an additional hour. The mixture was then stripped to C. at 0.2 Torr to give 424.5 parts of a product analyzing 93% B-(dimethuxyphosphinyloxy)crotonyl chloride, identified by elemental, infra-red spectrum and nuclear magnetic resonance analyses and by equivalent weight.

EXAMPLE 11 Preparation of crotonic acid, 3-hydr0xy-, cis, Z-butynylene bis(ester), bis(dimethyl phosphate) 4.3 parts of 1,4-butynediol were added to 25.8 parts of 3 (dimethoxyphosphinyloxy) crotonyl chloride (89% pure), as prepared in Example I, and parts of carbon tetrachloride. The reaction mixture was heated to reflux for approximately two hours, allowed to stand overnight then stripped in a rotary evaporator at C. giving 25 parts of the his ester in 72.5% yield. The product was further purified by dilution in carbon tetrachloride, washed with water, and saturated sodium carbonate solution, then dried over magnesium sulfate, filtered and stripped over the rotary evaporator. The identity of the compound was confirmed by infra-red spectrum analysis and by elemental analysis: percent by weight.

Calculated for P O C H P, 13.2; C1, 0. Found: P, 12.9;C1, 0.1.

EXAMPLE III In a manner similar to that of Example II, the acid chloride of Example I was reacted with 2,7-dimethyl-3,5-

octadiyne-2,7-diol to give crotomc acid, 3-hydroxy-, cis,

4 diester with 2,7-dimethyl-3,5-octadiyne-2,7-diol in 73% yield, the structure of which was confirmed by elemental analysis: percent by weight.

Calculated for P O C H P, 11.0; Cl, 0.45.

P, 11.3; C1, 0. Found:

EXAMPLE V Evaluation 0 subject bis crotonates on mites and aphids TABLE L-TOXICITY OF BIS CROTONATES ON MITES AND APHIDS Toxicity of his crotonates to corn earworms TABLE Il..-TOXICITY R?IIS CROTONATES ON CORN It is thus evident that the compounds of this invention are effective insecticides, the term insect including not only the members of the class Insecta, but also related or similar non-vertebrate animal organisms belonging to the allied classes of arthropods and including mites, ticks, spiders, wood lice, and the like.

The compounds of this invention can be employed for insecticidal purposes by the use of any of the methods which are conventionally employed in that art. For example, the compounds can either be sprayed or otherwise applied in the form of a solution or dispersion, or they can be absorbed on an inert, finely-divided solid and applied as a dust. Useful solutions for application by spraying, brushing, dipping, and the like, can be prepared by using as the solvent any of the well-known inert horticultural carriers, including neutral hydrocarbons such as kerosene and other light mineral oil distillates of intermediate viscosity and volatility. Adjuvants, such as spreading or wetting agents, can also be included in the solutions, representative materials of this character being fatty acid soaps, rosin salts, saponins, gelatin, casein, long-chain fatty alcohols, alkyl acid sulfonates, longchain alkyl sulfonates, phenol ethylene oxide condensates, ammonium salts, and the like. These solutions can be employed as such, or, more preferably, they can be dispersed or emulsified in Water and the resulting aqueous dispersion or emulsion applied as a spray. Solid carrier materials which can be employed include talc, bentonite, lime gypsum, pyrophyllite and similar inert solid diluents. If desired, the compounds of the present invention can be employed as an aerosol, as by dispersing the same into the atmosphere by means of a compressed gas.

The concentration of the compounds to be used with the above carriers is dependent upon many factors, including the carrier employed, the method and conditions of application, and the insect species to be controlled, a proper consideration and resolution of these factors being within the skill of those versed in the insecticide art. In general, however, the compounds of this invention are eflective in concentrations of from about 0.01% to 0.5% based upon the total weight of the composition, though under some circumstances as little as about 0.00001% or as much as 2% or even more of the compound can be employed with good results from an insecticidal standpoint. Concentrates suitable for sale for dilution in the field may contain as much as 25-50% by weight, or even more, of the insecticide.

When employed as insecticides, the compounds of this invention can be employed either as the sole toxic ingredient of the insecticidal composition or can be employed in conjunction with other insecticidally-active materials. Representative insecticides of this latter class include the naturally-occurring insecticides such as pyrethrum, rotenone, sabadilla, and the like, as well as the various synthetic insecticides, including DDT, benzene hexachloride, thiodiphenylarnine, cyanides, tetraethyl pyrophosphate, diethyl-p-nitrophenyl thiophosphate, dimethyl 2,2-dichloroviny1 phosphate, 1,2-dibromo-2,2-dichloroethyl dimethyl phosphate, azobenzene, and the various compounds of arsenic, lead and/or fluorine. The crotonates of the invention may also be employed with other pesticides such as fungicides or nematocides, or may be used along with fertilizers, plant hormones, and the like.

I claim as my invention:

1. A compound of the formula wherein R is alkyl of 14 carbon atoms or middle halogen-substituted alkyl of 1-4 carbon atoms, and R is a divalent organic radical of up to 8 carbons selected from the group consisting of alkenylene, alkynylene, monomiddle halogen-substituted alkenylene and mono-middle halogen-substituted alkynylene, the unsaturation occurring between any two carbon atoms of said organic radical except the carbon atom bonded to the oxygen atom of the oxycarbonyl moiety.

2. The compound of claim 1 wherein R is alkyl of 1-4 carbon atoms.

3. The compound of claim 2 wherein R is alkynylene of up to 8 carbon atoms.

4. The compound of claim 2 wherein R is alkenylene of up to 8 carbon atoms.

5. The compound of claim 1 wherein R is methyl.

6. The compound of claim 3 wherein R is methyl.

7. The compound of claim 4 wherein R is methyl.

8. Crotonic acid, 3-hydroxy-, cis, Z-butynylene bis- (ester), bis (dimethyl phosphate).

9. Crotonic acid, 3-hydroxy-, cis, 2-butenylene bis- (ester), bis(dimethyl phosphate).

10. Crotonic acid, 3-hydroXy-, cis, diester with 2,7- -dimethyl 3,5 octadiyne 2,7 diol, bis(dimethyl phosphate).

References Cited UNITED STATES PATENTS 3,157,686 11/1964 Pohlemann et al. 260-928 CHARLES B. PARKER, Primary Examiner. A. H. SUTTO, Assistant Examiner. 

